Etching method and plasma processing apparatus

ABSTRACT

A disclosed etching method includes (a) generating plasma of a processing gas in a chamber of a plasma processing apparatus. The plasma is generated in a state where a substrate is placed on a substrate support having a lower electrode in the chamber. The substrate has a film and a mask. The mask is provided on the film. The etching method further includes (b) etching the film by supplying ions from the plasma to the substrate by periodically applying a pulse of a voltage to a lower electrode. In the operation (b), a level of a voltage of the pulse is changed at least once such that an absolute value of a negative potential of the substrate has a tendency to increase according to progress of etching of the film.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Divisional of U.S. patent application Ser. No.17/474,120 filed on Sep. 14, 2021, which is based on and claims thebenefit of priority from Japanese Patent Application Nos. 2020-155518filed on Sep. 16, 2020, and 2021-128960 filed on Aug. 5, 2021, theentire contents of which are incorporated herein by reference.

FIELD

Exemplary embodiments of the present disclosure relate to an etchingmethod and a plasma processing apparatus.

BACKGROUND

A plasma processing apparatus is used in plasma processing on asubstrate. The plasma processing apparatus is provided with a chamberand a substrate holding electrode. The substrate holding electrode isprovided in the chamber. The substrate holding electrode holds thesubstrate placed on the main surface thereof. A type of such a plasmaprocessing apparatus is disclosed in Japanese Unexamined PatentPublication No. 2009-187975.

The plasma processing apparatus disclosed in Japanese Unexamined PatentPublication No. 2009-187975 is further provided with a radio frequencygeneration device and a DC negative pulse generation device. The radiofrequency generation device applies a radio frequency voltage to thesubstrate holding electrode. The radio frequency generation devicealternately switches between ON and OFF of the radio frequency voltage.The DC negative pulse generation device applies a DC negative pulsevoltage to the substrate holding electrode according to the timing of ONand OFF of the radio frequency voltage. In the plasma processingapparatus disclosed in Japanese Unexamined Patent Publication No.2009-187975, the energy of ions that are supplied to the substratebecomes the maximum when the DC negative pulse voltage is applied to thesubstrate holding electrode. The energy of the ions that are supplied tothe substrate becomes the minimum when the DC negative pulse voltage isnot applied to the substrate.

SUMMARY

In an exemplary embodiment, an etching method is provided. The etchingmethod includes placing a substrate on a substrate support provided in achamber of a plasma processing apparatus. The substrate has a film and amask. The mask is provided on the film. The etching method furtherincludes etching the film of the substrate placed on the substratesupport. The etching the film includes (a) generating plasma of aprocessing gas in the chamber. The etching the film further includes (b)etching the film by supplying ions from the plasma to the substrate byperiodically applying a pulse of a voltage to a lower electrode in thesubstrate support. In the operation (b), a level of a voltage of thepulse is changed at least once such that an absolute value of a negativepotential of the substrate has a tendency to increase according toprogress of etching of the film.

The foregoing summary is illustrative only and is not intended to be inany way limiting. In addition to the illustrative aspects, exemplaryembodiments, and features described above, further aspects, exemplaryembodiments, and features will become apparent by reference to thedrawings and the following detailed description.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a flow chart of an etching method according to an exemplaryembodiment.

FIG. 2 is a partially enlarged sectional view of a substrate of anexample to which the etching method shown in FIG. 1 is applied.

FIG. 3 schematically illustrates a plasma processing apparatus accordingto an exemplary embodiment.

FIGS. 4A to 4D illustrate examples of a temporal change of a pulse of avoltage.

FIG. 5 is a partially enlarged sectional view of a substrate of anexample to which the etching method shown in FIG. 1 is applied.

FIG. 6 is a graph showing a relationship between four time intervals anda selection ratio obtained in a first experiment.

FIG. 7 is a graph showing a relationship between a depth of an openingformed in a film EF and the maximum width of an opening in a film FBobtained in the first experiment.

FIG. 8 is a graph showing a relationship between the depth of theopening formed in the film EF and the maximum width of an opening in afilm FA obtained in the first experiment.

FIG. 9 is a graph showing a relationship between a duty ratio of a pulseNP and an etching rate of the film FA obtained in the first experiment.

FIG. 10 is a graph showing the relationship between the duty ratio ofthe pulse NP and an etching rate of a mask MK obtained in the firstexperiment.

DETAILED DESCRIPTION

Hereinafter, various exemplary embodiments will be described.

In an exemplary embodiment, an etching method is provided. The etchingmethod includes placing a substrate on a substrate support provided in achamber of a plasma processing apparatus. The substrate has a film and amask. The mask is provided on the film. The etching method furtherincludes etching the film of the substrate placed on the substratesupport. The etching the film includes (a) generating plasma of aprocessing gas in the chamber. The etching the film further includes (b)etching the film by supplying ions from the plasma to the substrate byperiodically applying a pulse of a voltage to a lower electrode in thesubstrate support. In the operation (b), a level of a voltage of thepulse is changed at least once such that an absolute value of a negativepotential of the substrate has a tendency to increase according toprogress of etching of the film.

In the above embodiment, when the depth of the opening formed in thefilm of the substrate is shallow, since the absolute value of thenegative potential of the substrate is relatively small, the film isetched by using ions having relatively low energy. Further, when thedepth of the opening formed in the film of the substrate is deep, sincethe absolute value of the negative potential of the substrate isrelatively large, the film is etched by using ions having relativelyhigh energy. Since the ions having relatively low energy, which are usedwhen the depth of the opening is shallow, suppress etching of the mask,the selectivity of etching of the film with respect to etching of themask is enhanced. Further, the ions having relatively low energy, whichare used when the depth of the opening is shallow, can suppressdeterioration in the verticality of the opening that is formed in thefilm. Further, the ions having relatively high energy, which are usedwhen the depth of the opening is deep, enhance the etching rate of thefilm, thereby enhancing the selectivity of the etching of the film withrespect to the etching of the mask. Further, the ions having relativelyhigh energy, which are used when the depth of the opening is deep,enhance the verticality of the opening that is formed in the film.Therefore, according to the above embodiment, the verticality of theopening that is formed in the film and the selectivity of the etching ofthe film with respect to the etching of the mask are enhanced.

In an exemplary embodiment, the pulse may be a pulse of a negativevoltage or a pulse of a negative direct-current voltage. In theoperation (b), an absolute value of the voltage of the pulse may beincreased at least once such that the absolute value of the voltage ofthe pulse has a tendency to increase according to the progress of theetching of the film.

In the above embodiment, when the depth of the opening that is formed inthe film of the substrate is shallow, a pulse of a negative voltagehaving a relatively low absolute value is supplied to the lowerelectrode, and the film is etched by using ions having relatively lowenergy. Further, when the depth of the opening that is formed in thefilm of the substrate is deep, a pulse of a negative voltage having arelatively high absolute value is supplied to the lower electrode, andthe film is etched by using ions having relatively high energy.

In an exemplary embodiment, a duty ratio of the pulse may be set to 20%or less in the operation (b).

In an exemplary embodiment, a duty ratio of the pulse may be decreasedat least once to have a tendency to decrease according to the progressof the etching of the film, in the operation (b). In an exemplaryembodiment, the duty ratio of the pulse may be decreased to have a ratioof 15% or more and 20% or less, in the operation (b). According to theembodiment, it becomes possible to further suppress the etching of themask while suppressing a decrease in the etching rate of the film.

In an exemplary embodiment, the duty ratio of the pulse may be stepwiseor gradually reduced in the operation (b).

In an exemplary embodiment, the level of the voltage of the pulse may bestepwise or gradually changed in the operation (b).

An etching method according to another exemplary embodiment includesplacing a substrate on a substrate support provided in a chamber of aplasma processing apparatus. The substrate has a film and a mask. Themask is provided on the film. The etching method further includesetching the film of the substrate placed on the substrate support. Theetching the film includes (a) generating plasma of a processing gas inthe chamber of the plasma processing apparatus. The etching the filmfurther includes (b) etching the film by periodically applying a pulseof a voltage to a lower electrode in the substrate support to supplyions from the plasma to the substrate. In the operation (b), a dutyratio of the pulse is decreased at least once to have a tendency todecrease according to progress of the etching of the film. In anexemplary embodiment, the pulse may be a pulse of a negative voltage ora pulse of a negative direct-current voltage.

In an exemplary embodiment, the film may include a silicon-containingfilm. The film may include a silicon-containing dielectric film. Thefilm may include a silicon oxide film. The film may further include asilicon nitride film. The mask may be formed of polycrystalline silicon,

In still another exemplary embodiment, a plasma processing apparatus isprovided. The plasma processing apparatus is provided with a chamber, asubstrate support, a gas supply, a plasma generator, a bias powersource, and a controller. The substrate support has a lower electrodeand provided in the chamber. The gas supply is configured to supply aprocessing gas into the chamber. The plasma generator is configured togenerate plasma from a gas in the chamber. The bias power source iselectrically connected to the lower electrode and configured toperiodically generate a pulse of a voltage. The controller is configuredto (a) control the gas supply and the plasma generator to generateplasma of the processing gas in the chamber. The controller isconfigured to (b) control the bias power source to periodically applythe pulse to the lower electrode to supply ions from the plasma to asubstrate on the substrate support, thereby etching a film of thesubstrate. In the control of the (b), the bias power source iscontrolled to change a level of a voltage of the pulse at least oncesuch that an absolute value of a negative potential of the substrate hasa tendency to increase according to progress of etching of the film. Inan exemplary embodiment, the bias power source may be configured togenerate, as the pulse, a pulse of a negative voltage or a pulse of anegative direct-current voltage.

Hereinafter, various exemplary embodiments will be described in detailwith reference to the drawings. In the drawings, the same or equivalentportions are denoted by the same reference symbols.

FIG. 1 is a flow chart of an etching method according to an exemplaryembodiment. The etching method (hereinafter referred to as a “methodMT”) shown in FIG. 1 is performed in order to etch a film of asubstrate.

FIG. 2 is a partially enlarged sectional view of a substrate of anexample to which the etching method shown in FIG. 1 is applied. Asubstrate W shown in FIG. 2 has a film EF and a mask MK. The film EF isetched in the method MT. The film EF may include a silicon-containingfilm and/or a silicon-containing dielectric film. The film EF mayinclude a silicon oxide film and/or a silicon nitride film. The mask MKis provided on the film EF. The mask MK has a pattern that istransferred to the film EF. The mask MK may be formed of any material aslong as the film EF is selectively etched with respect to the mask MK.In a case where the film EF includes a silicon oxide film and/or asilicon nitride film, the mask MK may be formed of polycrystallinesilicon.

The film EF may be a single-layer film or may be a multi-layer film. Inan embodiment, the film EF may include a film FA and a film FB. The filmFB is provided on the film FA, and the mask MK is provided on the filmFB. The film FA may be a silicon oxide film, and the film FB may be asilicon nitride film. In an embodiment, the substrate W may further havean underlying region UR. The film EF may be provided on the underlyingregion UR.

In the method MT, a plasma processing apparatus is used for etching ofthe film of the substrate. FIG. 3 is a diagram schematically showing aplasma processing apparatus according to an exemplary embodiment. In themethod MT, a plasma processing apparatus 1 shown in FIG. 3 may be used.The plasma processing apparatus 1 is a capacitively coupled plasmaprocessing apparatus. The plasma processing apparatus 1 is provided witha chamber 10. The chamber provides an internal space 10 s therein. Thecentral axis of the chamber 10 is an axis AX which extends in thevertical direction.

In an embodiment, the chamber 10 may include a chamber body 12. Thechamber body 12 has a substantially cylindrical shape. The internalspace 10 s is provided in the chamber body 12. The chamber body 12 isformed of, for example, aluminum. The chamber body 12 is electricallygrounded. A film having corrosion resistance is provided on the innerwall surface of the chamber body 12. The film having corrosionresistance may be a film formed of ceramic such as aluminum oxide oryttrium oxide.

A passage 12 p is provided in the side wall of the chamber body 12. Thesubstrate W passes through the passage 12 p when it is transferredbetween the internal space 10 s and the outside of the chamber 10. Thepassage 12 p is made to be able to be opened and closed by a gate valve12 g. The gate valve 12 g is provided along the side wall of the chamberbody 12.

The plasma processing apparatus 1 is further provided with a substratesupport 16. The substrate support 16 is configured to support thesubstrate W in the chamber 10. The substrate W may have a substantiallydisk shape. The substrate support 16 may be supported by a support 15.The support 15 extends upward from a bottom portion of the chamber body12. The support 15 has a substantially cylindrical shape. The support 15is formed of an insulating material such as quartz.

The substrate support 16 includes a lower electrode 18. The substratesupport 16 may further include an electrostatic chuck 20. The substratesupport 16 may further include an electrode plate 19. The electrodeplate 19 is formed of a conductive material such as aluminum. Theelectrode plate 19 has a substantially disk shape, and the central axisthereof is the axis AX. The lower electrode 18 is provided on theelectrode plate 19. The lower electrode 18 is formed of a conductivematerial such as aluminum. The lower electrode 18 has a substantiallydisk shape, and the central axis thereof is the axis AX. The lowerelectrode 18 is electrically connected to the electrode plate 19.

The lower electrode 18 provides a flow path 18 f therein. The flow path18 f is connected to a supply device for a heat exchange medium (forexample, a chiller unit). The supply device is provided outside thechamber 10. The flow path 18 f receives the heat exchange medium that issupplied from the supply device through a pipe 23 a. The heat exchangemedium flows through the flow path 18 f and is then returned to thesupply device through a pipe 23 b. The supply device configures atemperature adjusting mechanism of the plasma processing apparatus 1.

The electrostatic chuck 20 is provided on the lower electrode 18. Thesubstrate W is placed on the upper surface of the electrostatic chuck20. The electrostatic chuck 20 has a main body and an electrode. Themain body is formed of a dielectric. Each of the electrostatic chuck 20and the main body thereof has a substantially disk shape, and thecentral axis thereof is the axis AX. The electrode is a film havingelectrical conductivity and is provided in the main body. The electrodeis connected to a direct-current power source through a switch. When thevoltage from the direct-current power source is applied to theelectrode, an electrostatic attraction force is generated between theelectrostatic chuck 20 and the substrate W. Due to the generatedelectrostatic attraction force, the substrate W is attracted to theelectrostatic chuck 20 and held by the electrostatic chuck 20.

The substrate support 16 may support an edge ring ER that is mounted ona peripheral edge portion thereof. The edge ring ER may be formed ofsilicon, silicon carbide, or quartz. The substrate W is disposed on theelectrostatic chuck 20 and in a region surrounded by the edge ring ER.

The plasma processing apparatus 1 may be further provided with a gassupply line 25. The gas supply line 25 supplies a heat transfer gas (forexample, a He gas) from a gas supply mechanism to a gap between theupper surface of the electrostatic chuck 20 and the rear surface (lowersurface) of the substrate W.

The plasma processing apparatus 1 may be further provided with a tubularpart 28 and an insulating part 29. The tubular part 28 extends upwardfrom the bottom portion of the chamber body 12. The tubular part 28extends along the outer periphery of the support 15. The tubular part 28is formed of a conductive material and has a substantially cylindricalshape. The tubular part 28 is electrically grounded. The insulating part29 is provided on the tubular part 28. The insulating part 29 is formedof a material having insulation properties. The insulating part 29 isformed of ceramic such as quartz, for example. The insulating part 29has a substantially cylindrical shape. The insulating part 29 extendsalong the outer periphery of the electrode plate 19, the outer peripheryof the lower electrode 18, and the outer periphery of the electrostaticchuck 20.

The plasma processing apparatus 1 is further provided with an upperelectrode 30. The upper electrode 30 is provided above the substratesupport 16. The upper electrode 30 is supported on an upper portion ofthe chamber body 12 through a member 32. The member 32 is formed of amaterial having insulation properties. The upper electrode 30 and themember 32 close the upper opening of the chamber body 12.

The upper electrode 30 may include a ceiling plate 34 and a support 36.The lower surface of the ceiling plate 34 is a lower surface on theinternal space 10 s side and defines the internal space 10 s. Theceiling plate 34 may be formed of a low resistance conductor orsemiconductor with low Joule heat. In an embodiment, the ceiling plate34 is formed of silicon. A plurality of gas discharge holes 34 a areprovided in the ceiling plate 34. The plurality of gas discharge holes34 a penetrate the ceiling plate 34 in a plate thickness directionthereof.

The support 36 detachably supports the ceiling plate 34. The support 36is formed of a conductive material such as aluminum. The support 36provides a gas diffusion chamber 36 a therein. The support 36 is furtherprovided with a plurality of gas holes 36 b. The plurality of gas holes36 b extend downward from the gas diffusion chamber 36 a. The pluralityof gas holes 36 b communicate with the plurality of gas discharge holes34 a, respectively. The support 36 is further provided with a gasintroduction port 36 c. The gas introduction port 36 c is connected tothe gas diffusion chamber 36 a. A gas supply pipe 38 is connected to thegas introduction port 36 c.

A gas source group 40 is connected to the gas supply pipe 38 through avalve group 41, a flow rate controller group 42, and a valve group 43.The gas source group 40, the valve group 41, the flow rate controllergroup 42, and the valve group 43 configure a gas supply GS. The gassource group 40 includes a plurality of gas sources. The plurality ofgas sources of the gas source group 40 include sources of a plurality ofgases. Each of the valve group 41 and the valve group 43 includes aplurality of on-off valves. The flow rate controller group 42 includes aplurality of flow rate controllers. Each of the plurality of flow ratecontrollers of the flow rate controller group 42 is a mass flowcontroller or a pressure control type flow rate controller. Each of theplurality of gas sources of the gas source group 40 is connected to thegas supply pipe 38 through a corresponding on-off valve of the valvegroup 41, a corresponding flow rate controller of the flow ratecontroller group 42, and a corresponding on-off valve of the valve group43.

The plasma processing apparatus 1 may be further provided with a bafflemember 48. The baffle member 48 is provided between the tubular part 28and the side wall of the chamber body 12. The baffle member 48 may be aplate-shaped member. The baffle member 48 is configured, for example, byforming a film having corrosion resistance on the surface of a membermade of aluminum. The film having corrosion resistance may be a filmformed of ceramic such as yttrium oxide. A plurality of through-holesare provided in the baffle member 48. An exhaust port 12 e is providedbelow the baffle member 48 and in the bottom portion of the chamber body12. An exhaust device 50 is connected to the exhaust port 12 e throughan exhaust pipe 52. The exhaust device 50 has a pressure adjustingvalve, and a vacuum pump such as a turbo molecular pump.

The plasma processing apparatus 1 is further provided with a radiofrequency power source 61. The radio frequency power source 61 is apower source that generates radio frequency power HF for plasmageneration. The radio frequency power HF has a first frequency. Thefirst frequency is, for example, a frequency in the range of 27 to 100MHz. In an example, the first frequency is 40 MHz. The radio frequencypower source 61 is connected to the lower electrode 18 through a matcher61 m and the electrode plate 19 in order to supply the radio frequencypower HF to the lower electrode 18. The matcher 61 m has a matchingcircuit. The matching circuit of the matcher 61 m has variableimpedance. The impedance of the matching circuit of the matcher 61 m isadjusted to reduce the reflection from a load of the radio frequencypower source 61. The radio frequency power source 61 does not need to beelectrically connected to the lower electrode 18, and may be connectedto the upper electrode 30 through the matcher 61 m. The radio frequencypower source 61 configures a plasma generator in an embodiment.

The plasma processing apparatus 1 is further provided with a bias powersource 62. The bias power source 62 is connected to the lower electrode18 through the electrode plate 19. The bias power source 62 isconfigured to periodically generate a pulse NP of a voltage. Thepolarity of the voltage of the pulse NP may be either negative orpositive as long as the potential of the substrate W that is set byapplying the pulse NP to the lower electrode 18 is a negative potential.In an embodiment, the bias power source 62 generates a pulse of anegative voltage or a pulse of a negative direct-current voltage as thepulse NP of the voltage. The cycle of the pulse NP, that is, a timeinterval in which the pulse NP is generated, has a time length that isthe reciprocal of a second frequency. The second frequency is lower thanthe first frequency. The second frequency is, for example, a frequencyin the range of 1 kHz to 27 MHz. In an example, the second frequency is400 kHz. The ratio of a time during which the pulse NP is applied to thelower electrode 18 in the time length of one cycle, that is, the dutyratio, may be 20% or less.

In an embodiment, the bias power source 62 may be connected to the lowerelectrode 18 through a filter 62 f. The filter 62 f is a low-pass filterand reduces the radio frequency power HF that can flow into the biaspower source 62.

In an embodiment, the plasma processing apparatus 1 may be furtherprovided with an analyzer 72. The analyzer 72 performs spectroscopicanalysis of the plasma generated in the chamber 10. For example, theanalyzer 72 observes plasma emission through a window 74 provided in theside wall of the chamber body 12. The window 74 is made of an opticallytransparent member such as quartz.

The plasma processing apparatus 1 is further provided with a controller80. The controller 80 is a computer which includes a processor, astorage device, an input device, a display device, and the like, andcontrols each part of the plasma processing apparatus 1. Specifically,the controller 80 executes a control program stored in the storagedevice and controls each part of the plasma processing apparatus 1,based on recipe data stored in the storage device. The controller 80controls, for example, the gas supply GS, the exhaust device 50, theradio frequency power source 61, the bias power source 62, and the like.A process designated by the recipe data, for example, the method MT, isperformed in the plasma processing apparatus 1 under the control by thecontroller 80.

Hereinafter, the method MT will be described with reference to FIG. 1again. In the following description, the method MT will be described bytaking a case where the method MT is applied to the substrate W shown inFIG. 2 by using the plasma processing apparatus 1, as an example. Thesubstrate to which the method MT is applied may be a substrate differentfrom the substrate shown in FIG. 2 . Further, in the method MT, a plasmaprocessing apparatus different from the plasma processing apparatus 1may be used.

As shown in FIG. 1 , the method MT includes step STp and step STe. Instep STp, the substrate W is placed on the substrate support 16. StepSTe is performed in a state where the substrate W is placed on thesubstrate support 16. In step STe, the film EF is etched. Step STeincludes step ST1 and step ST2. Steps ST1 and ST2 are performed in astate where the substrate W is placed on the substrate support 16 thechamber 10.

In step ST1, plasma of the processing gas is generated in the chamber ofthe plasma processing apparatus. The processing gas is selectedaccording to the film type of the film EF to be etched. In a case wherethe film EF includes a silicon oxide film and/or a silicon nitride film,the processing gas may include a fluorocarbon gas. The processing gasmay include at least one of a rare gas such as argon gas, an oxygen gassuch as O₂ gas, and another fluorine-containing gas. In step ST1, theprocessing gas is excited in the chamber by the energy that is suppliedby the plasma generator. As a result, plasma is generated in thechamber.

In a case where the plasma processing apparatus 1 is used, thecontroller 80 controls the gas supply GS to supply the processing gasinto the chamber 10 in step ST1. Further, the controller 80 controls theexhaust device 50 to set the pressure in the chamber 10 to a designatedpressure. Further, the controller 80 controls the radio frequency powersource 61 to supply the radio frequency power HF. Under the control ofthe controller 80, plasma is generated from the processing gas in thechamber 10. The frequency of the radio frequency power HF during aperiod in which step STe is performed may be constant. The frequency ofthe radio frequency power HF during period in which step STe isperformed may be, for example, 40 MHz.

Step ST2 is performed when the plasma generated in step ST1 is presentin the chamber. Step ST2 may be performed at the same time as thegeneration of the plasma in step ST1. Step ST2 includes step ST21. Instep ST21, the pulse NP is applied to the lower electrode of thesubstrate support. Step ST21 is periodically repeated. That is, in stepST2, the pulse NP is periodically applied to the lower electrode of thesubstrate support. In step ST2, the ions from the plasma are supplied tothe substrate, whereby the film EF is etched.

In a case where the plasma processing apparatus 1 is used, thecontroller 80 controls the bias power source 62 to periodically applythe pulse NP to the lower electrode 18 in step ST2. A cycle, that is, atime interval, in which the pulse NP is applied to the lower electrode18 has a time length that is the reciprocal of the second frequency. Asdescribed above, the second frequency is, for example, a frequency inthe range of 1 kHz to 27 MHz. In an example, the second frequency is 400kHz. The ratio of a time during which the pulse NP is applied to thelower electrode 18 in the time length of one cycle, that is, the dutyratio, may be 20% or less.

In step ST2, each of one or more parameters of the pulse NP is changedaccording to the progress of etching of the film EF. Each of the one ormore parameters of the pulse NP is changed at least once during therepetition of step ST21. Each of the one or more parameters of the pulseNP may be stepwise or gradually changed during the repetition of stepST21. The one or more parameters of the pulse NP may include at leastone of the level of the voltage of the pulse NP and the duty ratio ofthe pulse NP.

In step ST2, the level of the voltage of the pulse NP may be changed atleast once such that the absolute value of the negative potential of thesubstrate W has a tendency to increase according to the progress of theetching of the film EF. In step ST2, the level of the voltage of thepulse NP may be stepwise or gradually changed such that the absolutevalue of the negative potential of the substrate W has a tendency toincrease according to the progress of the etching of the film EF.

FIGS. 4A to 4D are diagrams showing examples of a temporal change of thepulse of the voltage. In FIG. 4A, a stepwise change in the level of thevoltage of the pulse NP is shown. As shown in FIG. 4A, in step ST2, thelevel of the voltage of the pulse NP may be changed every two or morecycles. In FIG. 4B, a gradual change in the level of the voltage of thepulse NP is shown. As shown in FIG. 4B, in step ST2, the level of thevoltage of the pulse NP may be changed for each cycle.

In an embodiment, in step ST2, the absolute value of the negativevoltage or the negative direct-current voltage of the pulse NP may beincreased at least once to have a tendency to increase according to theprogress of the etching of the film EF. In step ST2, the absolute valueof the negative voltage or the negative direct-current voltage of thepulse NP may be stepwise or gradually increased to have a tendency toincrease according to the progress of the etching of the film EF.

In step ST2, the duty ratio of the pulse NP may be decreased at leastonce to have a tendency to decrease according to the progress of theetching of the film EF. In step ST2, the duty ratio of the pulse NP maybe stepwise or gradually decreased to have a tendency to decreaseaccording to the progress of the etching of the film EF. In FIG. 4C, astepwise decrease in the duty ratio of the pulse NP is shown. As shownin FIG. 4C, in step ST2, the duty ratio of the pulse NP may be reducedevery two or more cycles. In FIG. 4D, a gradual change in the duty ratioof the pulse NP is shown. As shown in FIG. 4D, in step ST2, the dutyratio of the pulse NP may be reduced for each cycle.

In an embodiment, in step ST2, the duty ratio of the pulse NP may bereduced to have a ratio in the range of 15% or more and 20% or less.During a period in which step ST2 is performed, the absolute value ofthe voltage of the pulse NP and the duty ratio of the pulse NP may bechanged at the same time, or may be changed at different timings.

In step ST2, the controller 80 controls the bias power source 62 tochange each of the one or more parameters of the pulse NP at least onceaccording to the progress of the etching of the film EF. In step ST2,the controller 80 may control the bias power source 62 to change thelevel of the voltage of the pulse NP at least once such that theabsolute value of the negative potential of the substrate W has atendency to increase according to the progress of the etching of thefilm EF. In a case where the voltage of the pulse NP has a negativepolarity, in step ST2, the controller 80 may control the bias powersource 62 to increase the absolute value of the voltage of the pulse NPat least once such that the absolute value of the voltage of the pulseNP has a tendency to increase according to the progress of the etchingof the film EF. In step ST2, the controller 80 may control the biaspower source 62 to decrease the duty ratio of the pulse NP at least oncesuch that the duty ratio of the pulse NP has a tendency to decreaseaccording to the progress of the etching of the film EF.

In an embodiment, step ST2 may include step ST22 in addition to stepST21. Step ST2 may further include step ST2 a and step ST2 b. In stepST2 a, it is determined whether or not a stop condition is satisfied.The stop condition is determined to be satisfied, for example, in a casewhere the number of repetitions of step ST21 reaches a predeterminednumber of times. The predetermined number of times may be designated asa part of the recipe data. When it is determined in step ST2 a that thestop condition is not satisfied, the determination in step ST2 b is thenperformed.

In step ST2 b, it is determined whether or not any of the one or moreparameters of the pulse NP has to be changed. A timing of a change ofeach of the one or more parameters of the pulse NP may be specified as apart of the recipe data. When it is determined in step ST2 b that noneof the one or more parameters of the pulse NP has to be changed, theprocessing proceeds to step ST21.

On the other hand, in a case where it is determined in step ST2 b thatany of the one or more parameters of the pulse NP has to be changed, theprocessing proceeds to step ST22. In an example, in a case where thenumber of times in which the pulse NP of the same level continues to beoutput (that is, the number of consecutive cycles in which the pulse NPof the same level is output) has reached a predetermined number oftimes, the processing proceeds to step ST22. In another example, in acase where, from the emission intensity of each of the lights of aplurality of wavelengths, which are acquired by the analyzer 72, it isdetermined that the type of the film that is etched has been switched,the processing proceeds to step ST22. For example, in a case where thefilm EF includes a laminate of a silicon oxide film and a siliconnitride film, when the silicon oxide film is etched, the emissionintensity at a wavelength of 483 nm is large, and when the siliconnitride film is etched, the emission intensity at the wavelength of 387nm is large. In a case where the film EF includes a laminate of asilicon oxide film and a silicon nitride film, a timing at which thetype of the film that is etched is switched is identified by observingthe emission intensities of the lights of these wavelengths, and stepST22 is performed at such a timing.

In step ST22, the parameter of the pulse NP to be changed is changed. Ina case where the level of the voltage of the pulse NP is the parameterto be changed, the level is changed in step ST22. For example, in a casewhere the voltage of the pulse NP has a negative polarity, the absolutevalue of the voltage of the pulse NP is increased in step ST22. In acase where the duty ratio of the pulse NP is the parameter to bechanged, the duty ratio is reduced in step ST22. The change value of theparameter to be changed, of the pulse NP, may be specified as a part ofthe recipe data. After step ST22, the processing proceeds to step ST21.

After step ST21 is periodically repeated, when it is determined in stepST2 a that the stop condition is satisfied, step ST2 ends and the methodMT ends. FIG. 5 is a partially enlarged sectional view of a substrate ofan example to which the etching method shown in FIG. 1 is applied. Instep ST2, the film EF is etched to transfer the pattern of the mask MKthereto. As a result, an opening is formed in the film EF. In step ST2,as shown in FIG. 5 , the film EF may be etched to partially expose theunderlying region UR.

In the method MT, when the depth of the opening formed in the film EF ofthe substrate W is shallow, since the absolute value of the negativepotential of the substrate W is relatively small, the film EF is etchedby using ions having relatively low energy. Further, when the depth ofthe opening formed in the film EF of the substrate W is deep, since theabsolute value of the negative potential of the substrate W isrelatively large, the film EF is etched by using ions having relativelyhigh energy. The ions having relatively low energy, which are used whenthe depth of the opening is shallow, suppress etching of the mask MK,and therefore, the selectivity of the etching of the film EF withrespect to the etching of the mask MK is enhanced. Further, the ionshaving relatively low energy, which are used when the depth of theopening is shallow, can suppress deterioration in the verticality of theopening that is formed in the film EF. Further, the ions havingrelatively high energy, which are used when the depth of the opening isdeep, enhance the etching rate of the film EF, thereby enhancing theselectivity of the etching of the film EF with respect to the etching ofthe mask MK. Further, the ions having relatively high energy, which areused when the depth of the opening is deep, enhance the verticality ofthe opening which is formed in the film EF. Therefore, according to themethod MT, the verticality of the opening that is formed in the film EFand the selectivity of the etching of the film EF with respect to theetching of the mask MK are enhanced.

In an embodiment, the voltage of the pulse NP that is periodicallyapplied has a negative polarity. In a case where the absolute value ofthe voltage of the pulse NP that is periodically applied has a tendencyto increase, when the depth of the opening formed in the film EF of thesubstrate W is shallow, the pulse NP of a negative voltage having arelatively low absolute value is supplied to the lower electrode 18.Therefore, the film EF is etched by using the ions having relatively lowenergy. Further, when the depth of the opening formed in the film EF isdeep, the pulse NP of a negative voltage having a relatively highabsolute value is supplied to the lower electrode 18, and the film EF isetched by using the ions having relatively high energy.

In a case where the duty ratio of the pulse NP that is periodicallyapplied has a tendency to decrease, the etching rate of the mask MKdecreases according to the progress of the etching of the film EF.Therefore, the selectivity of the etching of the film EF with respect tothe etching of the mask MK is enhanced. Further, in a case where theduty ratio of the pulse NP is reduced to have a ratio of 15% or more and20% or less, it becomes possible to further suppress the etching of themask MK while suppressing a decrease in the etching rate of the film EF.

While various exemplary embodiments have been described above, variousadditions, omissions, substitutions and changes may be made withoutbeing limited to the exemplary embodiments described above. Elements ofthe different embodiments may be combined to form another embodiment.

For example, a first period and a second period are alternatelyrepeated, and the power level of the radio frequency power HF in thesecond period may be set to be lower than the power level of the radiofrequency power HF in the first period. In the second period, the powerlevel of the radio frequency power HF may be set to zero. That is, thesupply of the radio frequency power HF may be stopped in the secondperiod. Further, the absolute value of the voltage of the pulse NP thatis periodically applied in the second period may be set to be lower thanthe absolute value of the voltage of the pulse NP that is periodicallyapplied in the first period. The application of the pulse NP may bestopped in the second period. In a case where the film that is etched inthe method MT is a silicon oxide film, the reciprocal of the time lengthof one cycle that includes the first period and the second period, thatis, a pulse frequency may be 2 kHz. In a case where the film that isetched in the method MT is a silicon nitride film, the pulse frequencymay be 5 kHz or higher and 10 kHz or lower.

Further, in the method MT, as long as one or more parameters of thepulse NP that is periodically applied to the lower electrode of thesubstrate support can be changed, any plasma processing apparatus may beused. As such a plasma processing apparatus, an inductively coupledplasma processing apparatus, an electron cyclotron resonance (ECR)plasma processing apparatus, or a plasma processing apparatus thatgenerates plasma by using surface waves such as microwaves isexemplified.

Hereinafter, various experiments performed for the evaluation of themethod MT will be described. The present disclosure is not limited bythese experiments.

First Experiment

In a first experiment, the method MT was applied to a plurality ofsample substrates that are the same as the substrate W shown in FIG. 2by using the plasma processing apparatus 1. In each of the samplesubstrates, the mask MK was a mask formed from a polycrystalline siliconfilm. The film FA was a silicon oxide film, and the film FB was asilicon nitride film. In the first experiment, the films EF of theplurality of sample substrates were etched under the conditions that theetching time (the time length in step ST2) and the absolute value of thenegative direct-current voltage of the pulse NP are different. Otherconditions of step ST1 and step ST2 are shown below.

<Conditions of Step ST1 and Step ST2>

-   -   Radio frequency power HF: 40 MHz, 1500 W    -   Second frequency of pulse NP: 400 kHz    -   Duty ratio of pulse NP: 15%    -   Processing gas: mixed gas that includes a fluorocarbon gas, an        O₂ gas, and an argon gas

In the first experiment, the selection ratios in four time intervalsfrom the start of etching were obtained from the etching result of thefilm EF of each sample substrate. The four time intervals were a timeinterval from 0 seconds to 60 seconds, a time interval from 60 secondsto 120 seconds, a time interval from 120 seconds to 180 seconds, and atime interval from 180 seconds to 240 seconds with the point in time ofthe start of etching as a reference. The selection ratio was obtained bydividing the etching rate of the film EF by the etching rate of the maskMK. The relationship between the four time intervals and the selectionratio is shown in FIG. 6 . As shown in FIG. 6 , when the elapsed timefrom the start of etching is short, that is, when the opening formed inthe film EF is shallow, it was confirmed that a high selection ratio wasobtained by using the pulse NP of a negative direct-current voltagehaving a small absolute value. Further, when the elapsed time from thestart of etching is long, that is, when the opening formed in the filmEF is deep, it was confirmed that a high selection ratio was obtained byusing the pulse NP of a negative direct-current voltage having a largeabsolute value. From this, it was confirmed that a high selection ratiocould be obtained by increasing the absolute value of the voltage of thepulse NP at least once such that the absolute value of the voltage ofthe pulse NP has a tendency to increase, in step ST2.

Further, in the first experiment, from the etching result of the film EFof each sample substrate, the relationship between the depth of theopening formed in the film EF and each of the maximum width (Bowing CD)of the opening in the film FA and the maximum width (Bowing CD) of theopening in the film FB was obtained. FIG. 7 is a graph showing therelationship between the depth of the opening formed in the film EF andthe maximum width (Bowing CD) of the opening in the film FB. FIG. 8 is agraph showing the relationship between the depth of the opening formedin the film EF and the maximum width (Bowing CD) of the opening in thefilm FA. As shown in FIGS. 7 and 8 , when the depth of the openingformed in the film EF was shallow, the dependence of the Bowing CD ofeach of the film FA and the film FB on the absolute value of the voltageof the pulse NP was small. When the depth of the opening formed in thefilm EF was deep, the larger the absolute value of the voltage of thepulse NP was, the smaller the Bowing CD of each of the film FA and thefilm FB became. From this, it was confirmed that the high selectionratio and the high verticality of the opening of the film EF could beobtained by increasing the absolute value of the voltage of the pulse NPat least once such that the absolute value of the voltage of the pulseNP has a tendency to increase, in step ST2.

Second Experiment

In a second experiment, the method MT was applied to a plurality ofsample substrates by using the plasma processing apparatus 1. Each ofthe plurality of sample substrates used in the second experiment was asample substrate having the same configuration as the sample substrateused in the first experiment. In the second experiment, the films EF ofthe plurality of sample substrates were etched under the conditions thatthe absolute value of the voltage of the pulse NP and the duty ratio aredifferent. Other conditions of step ST1 and step ST2 are shown below.

<Conditions of Step ST1 and Step ST2>

-   -   Radio frequency power HF: 40 MHz, 1500 W    -   Second frequency of pulse NP: 400 kHz    -   Processing gas: mixed gas that includes a fluorocarbon gas, an        O₂ gas, and an argon gas

In the second experiment, from the etching results of the plurality ofsample substrates, the relationship between the duty ratio of the pulseNP and each of the etching rate of the film FA and the etching rate ofthe mask MK was obtained. FIG. 9 shows the relationship between the dutyratio of the pulse NP and the etching rate of the film FA. FIG. 10 showsthe relationship between the duty ratio of the pulse NP and the etchingrate of the mask MK. As shown in FIG. 10 , the etching rate of the maskMK decreased according to a decrease in the duty ratio of the pulse NP.As shown in FIG. 9 , a decrease in the etching rate of the film FAaccording to a decrease in the duty ratio of the pulse NP was small aslong as the duty ratio of the pulse NP was decreased in the range from20% to 15%. Therefore, it was confirmed that the selectivity wasincreased in a case where the duty ratio of the pulse NP that isperiodically applied has a tendency to decrease. Further, in a casewhere the duty ratio of the pulse NP is reduced to have a ratio of 20%or more and 15% or less, it was confirmed that it became possible tofurther suppress the etching of the mask MK while suppressing a decreasein the etching rate of the film EF.

From the foregoing description, it will be appreciated that variousembodiments of the present disclosure have been described herein forpurposes of illustration, and that various modifications may be madewithout departing from the scope and spirit of the present disclosure.Accordingly, the various embodiments disclosed herein are not intendedto be limiting, with the true scope and spirit being indicated by thefollowing claims.

What is claimed is:
 1. A plasma processing apparatus comprising: achamber; a substrate support having a lower electrode and provided inthe chamber; a gas supply configured to supply a processing gas into thechamber; a plasma generator configured to generate plasma from a gas inthe chamber; a bias power source electrically connected to the lowerelectrode and configured to periodically generate a pulse of a voltage;and a controller configured to control the gas supply, the plasmagenerator, and the bias power source, wherein the controller isconfigured to (a) control the gas supply and the plasma generator togenerate plasma of the processing gas in the chamber, and (b) controlthe bias power source to periodically apply the pulse to the lowerelectrode to supply ions from the plasma to a substrate on the substratesupport, thereby etching a film of the substrate, and in said (b), thebias power source is controlled to change a level of a voltage of thepulse at least once such that an absolute value of a negative potentialof the substrate has a tendency to increase according to progress ofetching of the film.
 2. The plasma processing apparatus according toclaim 1, wherein the bias power source is configured to generate, as thepulse, a pulse of a negative voltage or a pulse of a negativedirect-current voltage, and to increase an absolute value of the voltageof the pulse at least once such that the absolute value of the voltageof the pulse has a tendency to increase according to the progress of theetching of the film, in said (b).
 3. The plasma processing apparatusaccording to claim 1, wherein the bias power source is configured to seta duty ratio of the pulse to 20% or less, in said (b).
 4. The plasmaprocessing apparatus according to claim 1, wherein the bias power sourceis configured to decrease a duty ratio of the pulse at least once suchthat the duty ratio of the pulse has a tendency to decrease according tothe progress of the etching of the film, in said (b).
 5. The plasmaprocessing apparatus according to claim 4, wherein the bias power sourceis configured to decrease the duty ratio of the pulse such that the dutyratio of the pulse has a ratio of 15% or more and 20% or less, in said(b).
 6. The plasma processing apparatus according to claim 4, whereinthe bias power source is configured to reduce the duty ratio of thepulse stepwise or gradually, in said (b).
 7. The plasma processingapparatus to claim 1, wherein the bias power source is configured tochange the level of the voltage of the pulse stepwise or gradually, insaid (b).
 8. A plasma processing apparatus comprising: a chamber; asubstrate support having a lower electrode and provided in the chamber;a gas supply configured to supply a processing gas into the chamber; aplasma generator configured to generate plasma from a gas in thechamber; a bias power source electrically connected to the lowerelectrode and configured to periodically generate a pulse of a voltage;and a controller configured to control the gas supply, the plasmagenerator, and the bias power source, wherein the controller isconfigured to (a) control the gas supply and the plasma generator togenerate plasma of the processing gas in the chamber, and (b) controlthe bias power source to periodically apply the pulse to the lowerelectrode to supply ions from the plasma to a substrate on the substratesupport, thereby etching a film of the substrate, and in said (b), thebias power source is controlled to decrease a duty ratio of the pulse atleast once such that the duty ratio of the pulse has a tendency todecrease according to progress of the etching of the film.
 9. The plasmaprocessing apparatus to claim 8, wherein the pulse is a pulse of anegative voltage or a pulse of a negative direct-current voltage